Coating composition and articles made therefrom

ABSTRACT

The instant invention provides an aqueous dispersion, a coating composition, coating layers and coated article made therefrom. The coating composition according to the present invention comprises: (1) the inventive aqueous dispersion comprising the melt blending product of: (a) from 50 to 99 percent by weight of one or more polyethylene terephthalate resins, based on the total solid content of the dispersion; (b) from 1 to 50 percent by weight of one or more stabilizing agents comprising at least one second polyester, based on the total solid content of the dispersion, wherein said second polyester (i) has a carboxylic acid group and an acid number equal to or greater than 15, based on the solid content of the second polyester; or (ii) is a self-dispersing sulfopolyester; (c) one or more neutralizing agents; and (d) from 15 to 90 percent by weight of water, based on the total weight of the dispersion; wherein said dispersion has a solid content of 10 to 85 percent, based on the total weight of the dispersion; and (2) optionally one or more cross-linking agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of theU.S. application Ser. No. 12/559,056, filed on Sep. 14, 2009, now U.S.Pat. No. 8,063,128, entitled “AQUEOUS DISPERSION, ITS PRODUCTION METHOD,AND ITS USE,” which is a continuation application of the U.S. patentapplication Ser. No. 10/925,693, filed on Aug. 25, 2004, and now U.S.Pat. No. 7,803,865 B2, which is entitled “AQUEOUS DISPERSION, ITSPRODUCTION METHOD, AND ITS USE,” the teachings of which are incorporatedby reference herein, as if reproduced in full hereinbelow, which claimspriority to the U.S. Provisional Application Ser. No. 60/497,527, filedon Aug. 25, 2003, entitled “FROTHS AND DURABLE FOAMS OF DISPERSED OLEFINPOLYMERS AND ARTICLES PREPARED FROM SAME,” and the U.S. ProvisionalApplication Ser. No. 60/548,493, filed on Feb. 27, 2004, entitled “FROTHAND DURABLE FOAM OF DISPERSED OLEFIN POLYMERS, METHODS OF MAKING FOAMAND ARTICLES PREPARED FROM SAME,” the teachings of which areincorporated by reference herein, as if reproduced in full hereinbelow.

FIELD OF INVENTION

The instant invention relates to a coating composition and articles madetherefrom.

BACKGROUND OF THE INVENTION

The application of various treatment and pretreatment solutions tometals to retard or inhibit corrosion is well established. This isparticularly true in the area of metal food and beverage cans as well asnon-food metal containers. Coatings are applied to the interior of suchcontainers to prevent the contents from contacting the metal parts ofthe container. Contact between the metal and the food or beverage aswell as non-food substances can lead to corrosion of the metalcontainer, which can then contaminate the food or beverage or thenon-food contents of such metal containers. Corrosion is particularlyproblematic when food and beverage products are highly acidic natureand/or are having a high salt content such as a rhubarb-based productsor isotonic drinks. Also strong alkaline contents of non-food substancessuch as hair-dye may react with metal, for example aluminum, parts ofcontainers. The coatings applied, for example, to the interior of foodand beverage cans also helps prevent corrosion in the head space of thecans, which is the area between the fill line of the food product andthe can lid. The coatings may be applied to the outside of metalcontainers to provide protection against the external environment or toprovide a decorative layer including fillers and/or pigments. Inaddition to corrosion protection, coatings for food and beverage cansshould be non-toxic and inert, and, if applied to the internal surface,should not adversely affect the taste or appearance, e.g. color, of thefood or beverage in the can or contribute to a contamination of thecontents of the can. Resistance to “popping”, “blushing” and/or“blistering” is also desired. Certain coatings are particularlyapplicable for application onto coiled metal stock, such as the coiledmetal stock from which the ends of cans are made, “can end stock” andvalve cups, e.g. top ends of aerosol cans. Since coatings designed foruse on can end stock are applied prior to the ends being cut and stampedout of the coiled metal stock, they are also typically flexible and/orextensible. For example, can end stock is typically coated on bothsides. Thereafter, the coated metal stock is punched and may be beadedor bent. It may also be scored for the “pop-top” opening and the pop-topring is then attached with a pin that is separately fabricated. The endis then attached to the can body by an edge rolling process.Accordingly, the coating applied to the can end stock typically has acertain degree of toughness and flexibility, such that it can withstandextensive fabrication processes, in addition to some or all of the otherdesirable features discussed above. Various coatings such as epoxy-basedand polyvinyl chloride-based, e.g. organosol type, coatings have beenused in the past to coat the interior of metal cans to preventcorrosion. However, there is a need for food and beverage can liners aswell as non-food container liners that provide improved properties suchas having resistance to degradation in corrosive media as well asappropriate level of flexibility.

SUMMARY OF THE INVENTION

The instant invention provides an aqueous dispersion, a coatingcomposition, coating layers and coated article made therefrom.

In one embodiment, the instant invention provides an aqueous dispersioncomprising the melt blending product of: (a) from 50 to 99 percent byweight of one or more polyethylene terephthalate resins, based on thetotal solid content of the dispersion; (b) from 1 to 50 percent byweight of one or more stabilizing agents comprising at least one secondpolyester, based on the total solid content of the dispersion, whereinsaid second polyester (i) has a carboxylic acid group and an acid numberequal to or greater than 15, for example equal or greater than 20, basedon the solid content of the second polyester; or (ii) is aself-dispersing sulfopolyester; (c) one or more neutralizing agents; and(d) from 15 to 90 percent by weight of water, based on the total weightof the dispersion; wherein said dispersion has a solid content of 10 to85 percent, based on the total weight of the dispersion.

In an alternative embodiment, the instant invention further provides amethod for producing a aqueous dispersion comprising the steps of: (1)selecting one or more polyethylene terephthalate resins; (2) selectingone or more stabilizing agents comprising at least one second polyester,based on the total solid content of the dispersion, wherein said secondpolyester (i) has a carboxylic acid group and an acid number equal to orgreater than 15, for example equal or greater than 20, based on thesolid content of the second polyester; or (ii) is a self-dispersingsulfopolyester; (3) selecting one or more neutralizing agents; (4)melt-blending said one or more polyethylene terephthalate resins, one ormore stabilizing agents in the presence of water and one or moreneutralizing agents; (4) thereby producing an aqueous dispersion havinga solid content of 10 to 85 percent, based on the total weight of thedispersion.

In another alternative embodiment, the instant invention furtherprovides a coating composition comprising: (a) the inventive aqueousdispersion, as described hereinabove; (b) optionally one or morecross-linking agents; (c) optionally one or more selected from the groupconsisting of a polyolefin dispersion, acrylic latex, epoxy resindispersion, polyurethane dispersion, alkyd dispersion, vinyl acetatedispersion, and ethylene vinyl acetate dispersion.

In another alternative embodiment, the instant invention furtherprovides a coating layer comprising at least one or more film layersderived from the inventive coating composition, as describedhereinabove.

In another alternative embodiment, the instant invention furtherprovides a coated article comprising: (1) one or more substrates; (2) atleast one or more coating layers derived from the inventive coatingcomposition, as described hereinabove.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) selecting the inventive coatingcomposition, as described hereinabove; (3) applying said coatingcomposition to at least one surface of said substrate; (4) removing atleast a portion of the water from said the coating composition; (5)thereby forming one or more coating layers associated with saidsubstrate; and (6) thereby forming said coated substrate into a coatedarticle.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) forming said substrate into article; (3)selecting the coating composition, as described hereinabove; (4)applying said the coating composition to at least one surface of saidarticle; (5) removing at least a portion of the water from said thecoating composition; (6) thereby forming one or more coating layersassociated with at least one surface of said article; and (7) therebyforming said coated article.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the one or more polyethylene terephthalateresins have a glass transition temperature (T_(g)) of at least 30° C.;for example at least 40° C.; or in the alternative, at least 50° C.; orin the alternative, at least 60° C.; or in the alternative, at least 70°C.; or in the alternative in the range of 30 to 130° C.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is a pre-coated substrate.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is metal, wood, paper, plastic,glass, leather, and/or concrete.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the dispersion and/or the coating compositionderived therefrom further comprises a catalyst.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the one or more polyethylene terephthalateresins are linear saturated aromatic polyesters with a glass transitiontemperature of greater than 50° C. and an acid number of less than 5 mgKOH/g, and the second polyester is compatible with one or morepolyethylene terephthalate resins, such that a dispersion with a volumeaverage particle size of less than 5 microns is produced.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the aqueous dispersion and/or the coatingcompositions derived therefrom further comprise one or more bindercompositions such as acrylic latex, vinyl acrylic latex, styrene acryliclatex, vinyl acetate ethylene latex, polyurethane dispersion, alkyddispersion, epoxy dispersion, polyolefin dispersion, and combinationsthereof; optionally one or more fillers; optionally one or moreadditives such as catalysts, wetting agents, defoamers, flow agents,release agents, slip agents, anti-blocking agents, additives to masksulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters; optionally one or morelubricants such as fatty acid ester wax, silicon-based wax,fluorine-based wax, polyethylene or any other similar polyolefin wax,carnauba wax, lanolin wax or the like; optionally one or more corrosioninhibitors such as aluminum, and zinc: optionally one or more pigments,e.g. titanium dioxide, barium sulfate, mica, calcium carbonate, silica,zinc oxide, milled glass, aluminum trihydrate, talc, antimony trioxide,fly ash, and clay or the like; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, aromatic solvents and benzoate esters or thelike; optionally one or more dispersants, e.g. aminoalcohols, andpolycarboxylates; optionally one or more surfactants; optionally one ormore preservatives, e.g. biocides, mildewcides, fungicides, algaecides,and combinations thereof; optionally one or more thickeners, e.g.cellulosic based thickeners such as hydroxyethyl cellulose,hydrophobically modified alkali soluble emulsions (HASE thickeners suchas UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylatedurethane thickeners (HEUR); or optionally one or more additionalneutralizing agents, e.g. hydroxides, amines, ammonia, and carbonates;optionally one or more solvents or coalescing agents.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention provides an aqueous dispersion, a coatingcomposition, coating layers and coated article made therefrom.

The coating composition according to the present invention comprises:(1) the inventive aqueous dispersion comprising the melt blendingproduct of: (a) from 50 to 99 percent by weight of one or morepolyethylene terephthalate resins, based on the total solid content ofthe dispersion; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyester(i) has a carboxylic acid group and an acid number equal to or greaterthan 15, for example equal or greater than 20, based on the solidcontent of the second polyester; or (ii) is a self-dispersingsulfopolyester; (c) one or more neutralizing agents; and (d) from 15 to90 percent by weight of water, based on the total weight of thedispersion; wherein said dispersion has a solid content of 10 to 85percent, based on the total weight of the dispersion; and (2) optionallyone or more cross-linking agents.

Aqueous Dispersion

The aqueous dispersion according to the present invention comprises themelt blending product of: (a) from 50 to 99 percent by weight of one ormore polyethylene terephthalate resins, based on the total solid contentof the dispersion; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyester(i) has a carboxylic acid group and an acid number equal to or greaterthan 15, for example equal or greater than 20, based on the solidcontent of the second polyester; or (ii) is a self-dispersingsulfopolyester; (c) one or more neutralizing agents; and (d) from 15 to90 percent by weight of water, based on the total weight of thedispersion; wherein said dispersion has a solid content of 10 to 85percent, based on the total weight of the dispersion.

One or More Polyethylene Terephthalate Based Resins

The aqueous dispersion comprises from 50 to 99 percent by weight of oneor more polyethylene terephthalate resins based on the total weight ofthe solid content of the aqueous dispersion. All individual values andsubranges from 50 to 99 weight percent are included herein and disclosedherein; for example, the weight percent can be from a lower limit of 50,55, 60, 65, or 70 weight percent to an upper limit of 60, 65, 70, 75,80, 85, 90, 95, or 99 weight percent. For example, the aqueousdispersion may comprise from 55 to 95 percent by weight of one or morepolyethylene terephthalate resins, based on the total weight of thesolid content of the aqueous dispersion; or in the alternative, theaqueous dispersion may comprise from 60 to 90 percent by weight of oneor more polyethylene terephthalate resins, based on the total weight ofthe solid content of the aqueous dispersion; or in the alternative, theaqueous dispersion may comprise from 65 to 90 percent by weight of oneor more polyethylene terephthalate resins, based on the total weight ofthe solid content of the aqueous dispersion; or in the alternative, theaqueous dispersion may comprise from 75 to 95 percent by weight of oneor more polyethylene terephthalate resins, based on the total weight ofthe solid content of the aqueous dispersion. The aqueous dispersioncomprises at least one or more polyethylene terephthalate resins.

The one or more polyethylene terephthalate resins are polyesters andcopolyesters such as high molecular weight linear thermoplasticpolyesters, with at least some degree of intrinsic crystallinity, inwhich the dicarboxylic acid monomer component used is predominantlyterephthalic acid. These thermoplastic polyesters and copolyesters mayhave hydroxyl or carboxyl terminal groups; however the overall level offunctionality is very low and is typically not reported. It is typicallynot necessary to cros slink these polyesters in order to develop goodphysical properties. The polyesters and copolyesters are typicallyprepared by conventional polycondensation processes well known in theart, such as the process described in U.S. Pat. Nos. 2,901,466;2,465,319 and 3,047,539, incorporated herein by reference to the extentthat they disclose such processes. Typically, the thermoplasticpolyester or copolyester will have a glass transition temperature offrom 50 to 130° C., and a heat distortion temperature (ASTM D648 @ 264psi (1.82 MPa)) of from 60 to 120° C. The molecular weight of thethermoplastic polyesters and copolyesters are typically expressed interms of their intrinsic viscosities, which are in the range of from 0.5to 1.0 Dl/g, as measured at 25° C., in a solvent mixture consisting of60 wt % phenol and 40 wt % tetrachloroethane.

The dicarboxylic acid component of the thermoplastic polyesters andcopolyesters is predominantly terephthalic acid (at least 50 mole %based on the total moles of diacid). Preferably the thermoplasticpolyester or copolyester is composed of at least 80 mole % terephthalicacid, and most preferably at least 90 mole % terephthalic acid based onthe total moles of diacid. In addition to the terephthalic acid, thedicarboxylic acid component can have up to 50 mole % of anothermodifying dicarboxylic acid. The modifying dicarboxylic acid comonomersare used to modify properties such as melting point, T_(g), gaspermeability, clarity, flexibility, impact resistance, rate ofcrystallization, hydrolytic stability, and resistance to solvents andother chemicals. Preferably, the thermoplastic polyester or copolyestercontains less than 20 mole % of the modifying dicarboxylic acid, andmost preferably less than 10 mole % of the modifying dicarboxylic acid.Suitable modifying aromatic dicarboxylic acids include, but are notlimited to, those having up to about 20 carbon atoms, includingisophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-, 1,5-, 2,6-,2,7-naphthalenedicarboxylic acid, and trans-4,4′-stilbenedicarboxylicacid, and the esters thereof. Suitable modifying aliphatic dicarboxylicacids include, but are not limited to, malonic, succinic, glutaric,adipic, pimelic, suberic, azaleic, and dodecanedioic acids. Preferablyno more than 10 mole % of an aliphatic modifying dicarboxylic acid isused. The total mole % of the dicarboxylic component is 100 mole %.

The glycol component of the thermoplastic polyesters and copolyesters ofthe invention contains one or more of the following diols: ethyleneglycol, 2,3 butane diol, 1,4 butane diol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol (or mixtures of 1,3 and 1,4cyclohexanedimethanol, these may be cis or trans), and/or2,2,4,4-tetramethyl-1,3-cyclobutanediol (may be cis, trans, or a mixturethereof).

In an exemplary embodiment, the glycol component contains 10-100 mole %ethylene glycol (based on the total moles of diol). In another exemplaryembodiment, the glycol component contains 15-85 mole % ethylene glycol,and 15-85 mole % of one or more of the following diols: 1,4 butane diol1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or mixtures of 1,3and 1,4 cyclohexanedimethanol, may be cis or trans), and/or2,2,4,4-tetramethyl-1,3-cyclobutanediol (may be cis, trans, or a mixturethereof).

Additionally, the glycol component of the suitable copolyesters also canbe modified with up to 10 mole % of other glycols having 3-40 carbonatoms, preferably less than 5 mole % of the modifying glycol. Themodifying glycol comonomers are used to modify properties such asmelting point, T_(g), gas permeability, clarity, flexibility, impactresistance, rate of crystallization, hydrolytic stability, andresistance to solvents and other chemicals. Examples of suitablemodifying glycols include, but are not limited to, 1,2-propanediol,neopentyl glycol, 1,3-propanediol, polyethylene glycols,polytetramethylene glycols, p-xylene glycol, diethylene glycol,triethylene glycol, glycol, tripropylene glycol and higher polypropyleneglycols, butanediols, 1,5-pentanediol and other pentane diols,hexanediols, decanediols, and dodecanediols, glycerol,dipentaerythtritol, 1,3-butylene-ethylpropanediol,2-methyl-1,3-propanediol, 1,4-benzyldimethanol,2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), and mixtures thereof. In someembodiments, the aliphatic glycol may contain from 2 to about 8 carbonatoms, and mixtures thereof. The total mole % of the glycol component is100 mole %.

Exemplary thermoplastic polyesters are described, for example, in U.S.Pat. No. 2,936,296, U.S. Pat. No. 5,955,565, and U.S. Pat. No.5,859,116, incorporated herein by reference to the extent that suchthermoplastic polyesters are described. Additional details onthermoplastic polyesters can be found in “Handbook of Thermoplastics”,edited by Olagoke Olabisi and published by Marcel Dekker, Inc. (1997),ISBN 0-8247-9797-3. Pages 417-490. Suitable thermoplastic polyesters andcopolyesters are available, for example, from Eastman Chemical under thetrade names; CADENCE®, EASTAR®, SPECTAR®, PROVISTA®, DURASTAR®,EMBRACE®, & TRITAN®. This family of thermoplastic polyesters offers arange of molecular weights, glass transition temperatures and chemicalstructures that can offer advantageous properties in the water bornecoatings applications of this invention.

The thermoplastic polyesters and copolyester resins have very limitedambient temperature solubility, in traditional solvents that aresuitable for coating formulations. The current invention describes thediscovery that waterborne dispersions of such thermoplastic polyestersand copolyesters, at high solids, can be made and successfully appliedas liquids in high solids waterborne coating formulations.

Such thermoplastic polyesters and copolyesters include, but are notlimited to, for example, PCT, PBT, PCTG, PET, PETG, PCTA, PETA, and PTT.

Stabilizing Agent Comprising a Second Polyester

The aqueous dispersion further comprises at least one or morestabilizing agents comprising one or more second polyesters to promotethe formation of a stable dispersion. In one embodiment, the secondpolyester (i) has a carboxylic acid group and an acid number equal to orgreater than 15, for example equal or greater than 20, based on thesolid content of the second polyester; or (ii) is a self-dispersingsulfopolyester. In one embodiment, the second polyester has a carboxylicacid group and an acid number equal to or greater than 15, for examplegreater than 20. The aqueous dispersion comprises 1 to 50 percent byweight of one or more stabilizing agents, based on the total weight ofthe solid content of the dispersion. All individual values and subrangesfrom 1 to 50 weight percent are included herein and disclosed herein;for example, the weight percent can be from a lower limit of 1, 3, 5, 10weight percent to an upper limit of 15, 25, 35, 45, or 50 weightpercent. For example, the dispersion may comprise from 1 to 25; or inthe alternative, from 1 to 35; or in the alternative, from 1 to 40; orin the alternative, from 1 to 45 percent by weight of one or morestabilizing agents, based on the total weight of the solid content ofthe dispersion.

The carboxylated second polyester is a high acid, water dispersible,hydrophilic polyester, which is used as the primary stabilizing agentfor dispersing the first polyester resin. The carboxylated secondpolyester typically has an acid number in the range of from greater thanor equal to 15 mg KOH/g (based on resin solids), for example from 20 to80 mg KOH/g (based on resin solids). The carboxylic acid functionalityof the second polyester is critical to the present invention. Inproducing the waterborne dispersion, the acid functionality of thesecond polyester is neutralized with a suitable inorganic or organicbase to provide colloidal stability. The high acid stabilizing polyestermay also have hydroxyl functionality, but this is not required.Preferably the high acid stabilizing polyester has an OH number of atleast 2 mg KOH/g (based on resin solids), preferably 5 mg KOH/g orgreater, and most preferably 20 mg KOH/g or greater. The high acidstabilizing polyester may be produced by conventional polycondensationtechniques such as for example described in Zeno W. Wicks, Jr, Frank N.Jones, S. Peter. Pappas “Organic Coatings, Science and Technology,” pp246-257 (John Wiley & Sons, 1999, second edition) and references thereinor in Houben-Weyl, “Methoden der Organischen Chemie, Band E20,Makromolekulare Soffe, Polyester” pp 1405-1429. (Georg Thieme Verlag,Stuttgart 1987) and references therein. In one embodiment, a diol orpolyol and a di-carboxylic acid or polycarboxylic acid are charged intoa conventional polymerization vessel and reacted between about 150° C.and 280° C. for several hours. Optionally, an esterification catalystmay be used to decrease the reaction time. It may be preferable to use atwo-step process to provide a carboxyl functional polyester. In oneembodiment, an OH-functional polyester is first prepared so that thereis little, if any, free carboxylic acid and/or carboxylate functions,and which then in a subsequent step is reacted with a cyclicdicarboxylic anhydride, in a ring-opening and monoester-formingreaction, with free carboxylic acid and/or carboxylate groups then beingformed. The excess of OH functionality in the resin of the first step isdesigned in such a way that the final resin, after the reaction with thepolyacid functional molecules, will provide a carboxyl terminatedpolyester resin in which the acid number is typically in the range offrom equal to or greater than 15 mg KOH/g (based on resin solids), forexample from 20 to 80 mg KOH/g (based on resin solids).

The carboxylic acid component of the high acid stabilizing polyester maycontain one or more aliphatic, cycloaliphatic, araliphatic, and/oraromatic carboxylic acids with a COOH functionality of at least two, oranhydrides thereof. Suitable and typical dicarboxylic acids orpolycarboxylic acids, or their corresponding alkyl esters, that may beused to form the high acid stabilizing polyester include, but are notlimited to, saturated as well as unsaturated dicarboxylic acids such as,for example, but not limited to, maleic acid, maleic anhydride, malonicacid, fumaric acid, succinic acid, succinic anhydride, glutaric acid,adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid,dodecanedioic acids. phthalic acid, phthalic anhydride, 5-tert butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid,hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,azelaic acid, fumaric acid, sebacic acid, tetrachlorophthalic anhydride,chlorendic acid, isophthalic acid, trimellitic anhydride, terephthalicacid, naphthalene dicarboxylic acid, cyclohexane-dicarboxylic acid, andmixtures thereof.

The glycol component of the high acid stabilizing polyester may beethylene glycol, diethylene glycol, triethylene glycol and/or higherpolyethylene glycols, propylene glycol, dipropylene glycol, tripropyleneglycol and/or higher polypropylene glycols, 1,3-propanediol,1,4-butanediol and other butanediols, 1,5-pentanediol and/or otherpentane diols, hexanediols, decanediols, and/or dodecanediols, glycerol,trimethylolpropane, trimethylolethane, neopentyl glycol,pentaerythritol, cyclohexanedimethanol, a polyethylene or polypropyleneglycol having a molecular weight of about 500 or less,dipentaerythtritol, 1,3-butyleethylpropanediol,2-methyl-1,3-propanediol, 1,4-benzyldimethanol,2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), and mixtures thereof. In someembodiments, the aliphatic glycol may contain from 2 to 8 carbon atoms1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or mixtures of 1,3and 1,4 cyclohexanedimethanol, may be cis or trans),2,2,4,4-tetramethyl-1,3-cyclobutanediol (may be cis, trans, or a mixturethereof) 4,4′-dihydroxy-2,2′-diphenylpropane or mixtures thereof.

The composition of the high acid stabilizing polyester (secondpolyester) must be chosen so that it exhibits good compatibility withthe one or more polyethylene terephthalate resins. If the compatibilityis poor, a good water borne dispersion with small particle size(typically less than about 5 micron volume average particle sizediameter) and good stability may not be produced. In addition, resultingcoatings from such dispersions may have poor appearance and may showreduced performance in coatings evaluation tests because of lack ofcompatibility. One way to assess compatibility is to melt mix the one ormore polyethylene terephthalate resins and the second polyester at atemperature above their respective melting points. A blend with goodcompatibility will typically result in a relatively clear or translucentblend, while an incompatible blend will typically result in an opaque orhazy, white melt blend. There may be other methods to determinecompatibility such as morphology determination by optical microscopy ortransmission electron microscopy of the blend.

In another embodiment the stabilizing agent comprising a secondpolyester is a sulfopolyester that disperses directly in hot waterwithout the assistance of neutralizing agents. The sulfopolyesterconsists essentially of (a) a dicarboxylic acid component comprising oneor more sulfo monomers. Suitable sulfo monomers include, but are notlimited to dimethyl-5-sodiosulfoisophthalate, and5-sodiosulfoisophthalic acid. The dicarboxylic acid component typicallyalso contains one or more conventional dicarboxylic acids used in thepreparation of polyesters, including but not limited to, for example,isophthalic acid (b) a diol component consisting of one or more diolstypically used in the manufacture of polyesters, including, but notlimited to diethylene glycol, 1,4-cyclohexanedimethanol (cis or trans),1,3-cyclohexanedimethanol (cis or trans), and mixtures thereof. Thesulfo polyester will typically have a glass transition temperature (Tg)of between 20-60° C.

The useful sulfopolyesters in this invention are described in U.S. Pat.No. 3,546,008; U.S. Pat. No. 4,340,519; U.S. Pat. No. 3,734,874; U.S.Pat. No. 3,779,993; and U.S. Pat. No. 4,233,196 incorporated herein byreference to the extent that such sulfopolyesters disclosed. Usefulsulfopolyesters are available from Eastman Chemical, such as, forexample, Eastman AQ29, Eastman AQ38, and Eastman AQ55. Such suitablesulfopolyester are typically pre-neutralized.

The composition of the stabilizing polyester (second polyester) must bechosen so that it exhibits good compatibility with the first polyester.If the compatibility is poor, a good water borne dispersion with smallparticle size (typically less than about 5 micron volume averageparticle size diameter) and good stability may not be produced. Inaddition, resulting coatings from such dispersions may have poorappearance and may show reduced performance in coatings evaluation testsbecause of lack of compatibility. For example, if an aliphatic, highacid polyester (second polyester) is used to disperse an aromatic,hydrophobic first polyester, a poor dispersion will typically resultwith large particle size (typically greater than 5 micron volume averageparticle size diameter). One way to assess compatibility is to melt mixthe first polyester and the second polyester at a temperature abovetheir respective melting points. A blend with good compatibility willtypically result in a relatively clear or translucent blend, while anincompatible blend will typically result in an opaque or hazy, whitemelt blend. There may be other methods to determine compatibility suchas morphology determination by optical microscopy or transmissionelectron microscopy of the blend.

In selected embodiments, the stabilizing agent may optionally include asurfactant. Other stabilizing agents that may be used include, but arenot limited to, long chain fatty acids, fatty acid salts, or fatty acidalkyl esters having from 12 to 60 carbon atoms. In other embodiments,the long chain fatty acid or fatty acid salt may have from 12 to 40carbon atoms.

Additional stabilizing agents that may be useful in the practice of thepresent invention include, but are not limited to, cationic surfactants,anionic surfactants, or non-ionic surfactants. Examples of anionicsurfactants include, but are not limited to, sulfonates, carboxylates,and phosphates. Examples of cationic surfactants include, but are notlimited to, quaternary amines. Examples of non-ionic surfactantsinclude, but are not limited to, block copolymers containing ethyleneoxide and silicone surfactants. Stabilizing agents useful in thepractice of the present invention can be either external surfactants orinternal surfactants. External surfactants are surfactants that do notbecome chemically reacted into the base polymer during dispersionpreparation. Examples of external surfactants useful herein include, butare not limited to, salts of dodecyl benzene sulfonic acid and laurylsulfonic acid salt. Internal surfactants are surfactants that do becomechemically reacted into the base polymer during dispersion preparation.An example of an internal surfactant useful herein includes2,2-dimethylol propionic acid and its salts. Additional surfactants thatmay be useful in the practice of the present invention include cationicsurfactants, anionic surfactants, non-ionic surfactants, or combinationsthereof. Various commercially available surfactants may be used inembodiments disclosed herein, including: OP-100 (a sodium stearate),OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate), eachavailable from RTD Hallstar; UNICID 350, available from Baker Petrolite;DISPONIL FES 77-IS, DISPONIL TA-430, Disponil FES-32, and DiponilFES-993, each available from Cognis; RHODAPEX CO-436, SOPROPHOR 4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610, andRM-710, and SUPRAGIL MNS/90, each available from Rhodia; and TRITONQS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2, DOWFAX 8390, DOWFAX C6L,TRITON X-200, TRITON XN-455, TRITON H-55, TRITON GR-5M, TRITON BG-10,and TRITON CG-110, each available from The Dow Chemical Company,Midland, Mich. and ESPERSE grades E-100, E-506, E-328, E-355, and E-600,each available from Ethox Chemicals, LLC.

Additional stabilizing agents which could be used are solution orsuspension polymers consisting of ethylenically unsaturated monomerssuch as acrylic and/or methacrylic acid and their (C₁-C₃₀) esters oramides; acrylamide/methacrylamide and their N-substituted derivatives;acrylonitrile; styrene and substituted styrene derivatives.

Exemplary polymeric stabilizing agents include, but are not limited to,amphiphilic copolymer compositions, the copolymer comprising thereaction product of (i) from 5 to 95 wt. % of one or more hydrophilicmonomers and (ii) from 5 to 95 wt. % of one or more copolymerizableethylenically unsaturated hydrophobic monomers. These materials arewater soluble or emulsifiable, especially upon neutralization and canact as colloidal stabilizers. Exemplary stabilizing agents, for example,include, but are not limited to, butylacrylate and laurylmethacrylate.

Representative nonionic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions, include, but are not limited to,acrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, t-butylacrylamide, N methylolacrylamide,alkyl(meth)acrylates such as methyl(meth)acrylate, butyl acrylate andethylacrylate, vinyl monomers such as ethylene, styrene, divinylbenzene,di-isobutylethylene, vinyl acetate and N-vinyl pyrrolidone, and allylmonomers such as allyl(meth)acrylate.

Representative cationic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions include, but are not limited to,quaternary ammonium salts of amine functionalized monomers such asacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, t-butylacrylamide,N-methylolacrylamide, tributylammonium ethyl(meth)acrylate TBAEMA,DMAEMA, DMAPMAM, diallyldimethylammonium chloride (DADMAC),methylacrylamidopropyltrimethylammonium chloride (MAPTAC),acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl pyrrolidone,vinylimidazole, polyquaternium-11 and polyquaternium-4.

“Anionic” or “acid-containing monomer” suitable for production ofamphiphilic copolymer compositions include, but are not limited to,ethylenically unsaturated monomers containing carboxylic acid,phosphonic acid, phosphinic acid, sulfinic acid and sulfonic acidgroups. Suitable examples include (meth)acrylic acid, maleic acid,succinic acid, itaconic acid, vinyl phosphonic acid and vinylsulfonicacid.

In an alternative embodiment, one or more stabilizing agents may bebased on resins such as polyester, epoxy resins, polyamide resins, whichmight be reacted with acrylic resins or acrylic monomers to formpolyester acrylate, polyamide acrylates epoxy resin acrylates.

Polyester acrylates as stabilizing agents may be formed via in-situpolymerization of copolymerizable ethylenically unsaturated monomers inpresence of polyesters. Examples include ethylenically unsaturated mono-or polyfunctional acids, ethylenically unsaturated mono- orpolyfunctional acid esters, amides, nitriles as well as vinyl monomersand vinyl ester with a polyester in or without presence of a reactionfluid. Polyester acrylates in solvents can be dried according tosuitable methods known to those of ordinary skill in the art.

Suitable epoxy resins for producing stabilizing agents may be obtainedin accordance with conventional procedures well known to those ofordinary skill in the art by reacting a polyepoxide with a suitablepolynucleophile. Suitable epoxides include, but are not limited to,glycidyl ethers, and other epoxy group containing molecules. Suitablepolynucleophiles include, but are not limited to, polyhydric phenols,and poly phenols, polythiols, aliphatic polyalcohols or polybasic acidsor polyamines. Exemplary suitable epoxies, for example, include, but arenot limited to, glycidyl ether that contains at least two glycidyl ethergroups per polyglycidyl ether molecule (e.g. an at least diglycidylether) with a polyhydric phenol that contains at least two hydroxylgroups in the polyhydric polyphenol (e.g., at least dihydric phenol or adiphenol) in presence of a conventional catalyst at an elevatedtemperature with or without solvent present. Another class of epoxyresins may be obtained in accordance with conventional procedures wellknown to those of ordinary skill in the art by reacting, for example, apolyglycidyl ether that contains at least two glycidyl ether groups perpolyglycidyl ether molecule (e.g. an at least diglycidyl ether) with apolybasic acid that contains at least two carboxyl groups per polybasicacid molecule (e.g. an at least dibasic polycarboxylic acid) in presenceof a conventional catalyst at an elevated temperature with or withoutsolvent present.

Epoxy acrylates for producing stabilizing agents may be formed viain-situ polymerization of copolymerizable ethylenically unsaturatedmonomers in presence of epoxy resins. Examples include, but are notlimited to, ethylenically unsaturated mono- or polyfunctional acids,ethylenically unsaturated mono- or polyfunctional acid esters, amides,nitriles as well as vinyl monomers and vinyl ester with an epoxy resinsin or without presence of a reaction fluid. Alternatively a polymericacid functional acrylic resin can be reacted with an epoxy resin in thepresence of a suitable catalyst to form epoxy acrylate. Epoxy acrylatesin solvents can be dried according to suitable methods known to those ofordinary skill in the art. In one embodiment, the surfactant maycomprise the reaction product of an acid functionalized polyester and anepoxy resin.

In one embodiment, the stabilizing agent comprising a second polyester,which is acid functionalized oligomer derived from a PET basedpolyester.

Neutralizing Agent

The stabilizing agent may be partially or fully neutralized with aneutralizing agent. In certain embodiments, neutralization of thestabilizing agent, the second polyester, may be from 50 to 250 percenton a molar basis; or in the alternative, it may be from 50 to 200percent on a molar basis; or in the alternative, it may be from 50 to150 percent on a molar basis; or in the alternative, it may be from 50to 120 percent on a molar basis. For example, the neutralizing agent maybe a base, such as ammonium hydroxide, sodium hydroxide, or potassiumhydroxide. Other neutralizing agents can include lithium hydroxide orsodium hydroxide, for example. In another alternative, the neutralizingagent may, for example, be a carbonate. In another alternative, theneutralizing agent may, for example, be any amine such asmonoethanolamine, or 2-amino-2-methyl-1-propanol (AMP). Amines useful inembodiments disclosed herein may include diethanolamine,triethanolamine, and TRIS AMINO™ (each available from Angus), NEUTROL™TE (available from BASF), as well as triisopropanolamine,diisopropanolamine, and N,N-dimethylethanolamine (each available fromThe Dow Chemical Company, Midland, Mich.). Other useful amines mayinclude ammonia, monomethylamine, dimethylamine, trimethylamine,monoethylamine, diethylamine, triethylamine, mono-n-propylamine,butylamine, dibutylamine, tributylamine, dimethyl benzyl amine, dimethyln-propylamine, N-methanol amine, N-aminoethylethanolamine,N-methyldiethanolamine, monoisopropanolamine, N,N-dimethylpropanolamine, 2-amino-2-methyl-1-propanol, 1,2-diaminopropane,tris(hydroxymethyl)-aminomethane, ethylenediamineN,N,N′N′-tetrakis(2-hydroxylpropyl)ethylenediamine, N,N,N′,N′tetramethylpropanediamine, 3-methoxypropyl amine, imino bis-propyl amineand the like. In some embodiments, mixtures of amines or mixtures ofamines and other surfactants may be used. In one embodiment, theneutralizing agent may be a polymeric amine, e.g. diethylene triamine.Those having ordinary skill in the art will appreciate that theselection of an appropriate neutralizing agent depends on the specificcomposition formulated, and that such a choice is within the knowledgeof those of ordinary skill in the art. In one embodiment, amines withboiling points below 250° C. may be used as the neutralizing agents.

Fluid Medium

The aqueous dispersion further comprises a fluid medium. The fluidmedium may be any medium; for example, the fluid medium may be water.The aqueous dispersion comprises from 15 to 90 percent by weight ofwater, based on the weight of the dispersion; for example, thedispersion comprises from 20 to 85 percent by weight of water, based onthe weight of the dispersion; or in the alternative from 30 to 75percent by weight of water, based on the weight of the dispersion; or inthe alternative from 40 to 75 percent by weight of water, based on theweight of the dispersion; or in the alternative from 40 to 65 percent byweight of water, based on the weight of the dispersion. Water content ofthe dispersion may preferably be controlled so that the solids content(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester) is in the range of from 10 to 85 percentby weight, based on the weight of the dispersion. For example, thedispersion comprises from 20 to 70 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 25 to 70 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 35 to 70 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 35 to 65 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 40 to 70 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 40 to 65 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 45 to 65 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 50 to 70 percent by weight of solid contents(one or more polyethylene terephthalate resins plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion.

The fluid medium may optionally contain one or more suitable solvents.For example the one or more optional solvents include but are notlimited to, e.g. glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate, alcohols, ketones, glycol ether esters, mineralspirits, aromatic solvents and/or esters or the like; optionally one ormore dispersants, e.g. aminoalcohols, and/or polycarboxylates.

Additional Components

The aqueous dispersion of the present invention may optionally beblended with one or more binder compositions such as acrylic latex,vinyl acrylic latex, styrene acrylic latex, vinyl acetate ethylenelatex, epoxy dispersion, polyurethane dispersion, alkyd dispersion,polyolefin dispersion, and combinations thereof; optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, barium sulfate,mica, calcium carbonate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more co-solvents, e.g. glycols, glycol ether,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineralspirits, aromatic solvents and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or morepreservatives, e.g. biocides, mildewcides, fungicides, algaecides, andcombinations thereof; optionally one or more thickeners, e.g. cellulosicbased thickeners such as hydroxyethyl cellulose, hydrophobicallymodified alkali soluble emulsions (HASE thickeners such as UCARPOLYPHOBE TR-116) and hydrophobically modified ethoxylated urethanethickeners (HEUR); or optionally one or more additional neutralizingagents, e.g. hydroxides, amines, ammonia, and carbonates; optionally oneor more solvents or coalescing agents.

In addition, the aqueous dispersion may be blended with one or moredispersions, emulsions, suspensions, colloidal suspensions, and thelike.

For example the aqueous dispersion of the invention may be blended withpolyurethane dispersion, alkyd dispersion, epoxy dispersion, polyolefindispersion, vinyl acetate emulsion, acrylic emulsion, vinyl acetateethylene emulsion, and/or the like. The addition of the additionalcomponents, as described herein, may be achieved as part of the processfor making the dispersion, i.e. the additional components are addedwhile producing the aqueous dispersion; or in the alternative, theadditional components may added post aqueous dispersion production, i.e.the additional components are added into the aqueous dispersion afterthe dispersion is produced; or in the alternative, combinations thereof,i.e. additional components may be added during the process for makingthe dispersion and additionally such additional components are addedpost dispersion production as well.

Crosslinking Agent

The aqueous dispersion may optionally further comprise at least one ormore crosslinking agents to promote crosslinking and/or optionally oneor more catalyst to increase the rate of crosslinking. Such catalystsare generally known, and the selection of suitable catalyst typicallydepends on the selection of the crosslinking agent and other factorssuch as conditions for such crosslinking. Such catalysts include, butare not limited to, depending on type of crosslinker—strong acids, weakacids or compounds containing metals, such as dodecyl benzene sulfonicacid, p-toluene sulfonic acid, di-nonylnaphtalene disulfonic acid,methane sulfonic acid, phosphoric acid or weak acids such as ammonium orphosphonium salts or tin, bismuth, zirconium or aluminum chelatecompounds. Exemplary catalysts include, but are not limited to, NACURE™,K-Kure™ and K-Kat™, available from King Industries, CYCAT™ from CytecIndustries, and/or FASCAT™ from Arkema Inc. The aqueous dispersion ofthe instant invention comprises 0.5 to 50 percent by weight of one ormore crosslinking agents, based on the total weight of the solid contentof the dispersion. All individual values and subranges from 0.5 to 50weight percent are included herein and disclosed herein; for example,the weight percent can be from a lower limit of 0.5, 1, 3, 5, 10. 15, or20 weight percent to an upper limit of 10, 12, 15, 18, 20, 25, 30, 35,40, 45, or 50 weight percent. For example, the dispersion may comprisefrom 1 to 18; or in the alternative, from 1 to 15; or in thealternative, from 1 to 12; or in the alternative, from 1 to 10; or inthe alternative, from 1 to 20; or in the alternative, from 1 to 30; orin the alternative, from 1 to 40; or in the alternative, from 1 to 45;or in the alternative, from 1 to 50 percent by weight of one or morecrosslinking agents, based on the total weight of the solid content ofthe dispersion. In selected embodiments the crosslinking agent may, forexample, be phenol-formaldehyde resins, amino-formaldehyde resinsincluding, but not limited, to urea-formaldehyde resins, melamineformaldehyde resins, benzoguanamine formaldehyde resins, anhydrideresins, epoxy group containing resins such as epoxy resins, epoxy groupcontaining polyester or acrylic resins and blocked or unblockedisocyanate resins, and combinations of two or more thereof, providedthat the combinations of such crosslinkers is compatible.

Crosslinking agent may be a compound, which reacts with a reactivefunctional group contained in the dispersion formulation; therebyfacilitating their crosslinking. Such functional groups can be presentin both the one or more polyethylene terephthalate resins as well as thestabilizing agent comprising a second polyester.

For example, reactive functional groups include, but are not limited to,acid groups such as carboxylic acid groups, free or in the neutralizedform, or any functional groups having another active hydrogen by anothercomponent such as alcohol groups, amino groups, epoxy groups, or thelike.

Crosslinkable functional groups in the cross-linking agent are groupscapable of reacting with the reactive functional group of the firstpolyester or the stabilizing agent comprising a second polyester. Forexample, a carbodiimide group, an oxazoline group, an isocyanate group,an epoxy group, a methylol group, an aldehyde group, an acid anhydridegroup, a hydroxy group, an aziridinyl group or a silane group can beused in a crosslinker.

Another possibility of crosslinking acid functional groups is by use ofmultivalent metal ions by reaction of the aforementioned acid groupswith a multivalent metal ion containing substance, such as zinc oxide.

Carboxylic acids could also be crosslinked in reactions withmultifunctional olefinic unsaturated substances under catalysis of astrong acid. Multifunctional carbonates could also react with carboxylicacids to give ester linkages with liberation of carbon dioxide.

In the alternative, crosslinking may be accomplished via free radicalcrosslinking, initiated by addition of peroxides or via radiation, e.g.,electron beam.

With respect to crosslinkable functional groups, one or more may bepresent in a crosslinking agent. In the alternative, two or morecrosslinkable functional groups may be present in a single molecule.

The cross-linking agent having the above described crosslinkablefunctional group may be a waterdispersed or waterdispersible orwater-soluble substance. In one embodiment, exemplary crosslinkingagents include, but are not limited to, an aqueous monomeric orpolymeric substance, which contains two or more oxazoline groups,carbodiimide groups, epoxy groups, isocyanate groups, methylol groupsetc. or several of these per molecule.

An exemplary oxazoline crosslinking agent is an aqueous polymer havingtwo or more oxazoline groups in its molecules, substances can beobtained by polymerizing an oxazoline group-containing monomer and, asrequired, an ethylenic unsaturated monomer. Alternatively an oxazolinecrosslinking agent can also be obtained by reaction between a nitrilegroup and an aminoethanol group, dehydration of a hydroxylalkylamidegroup and the like.

Crosslinking agents having two or more carbodiimide groups can beproduced from diisocyanate compounds by a condensation reactionaccompanied by decarboxylation reaction of a diisocyanate compound.Examples of the diisocyanate compound include, but are not limited to,1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexanemethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate,isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate,methylcyclohexane diisocyanate, and tetramethylxylylene diisocyanate andthe like. These compounds may also be used as mixtures.

Monofunctional isocyanates may be included to control the resinmolecular chain length such as phenyl isocyanate, tolyl isocyanate,cyclohexylisocyanate, dimethylphenyl isocyanate, butylisocyanate, andnaphthyl isocyanate are useful.

Diisocyanate substances may be partially reacted with aliphaticcompounds, alicyclic compounds, or aromatic compounds having a hydroxylgroup, an imino group, an amino group, a carboxyl group, a mercaptogroup, an epoxy group, and the like.

In the condensation reaction accompanied by decarboxylation of adiisocyanate compound, a carbodiimidization catalyst can be used. Usableas such a catalyst are, for example, phospholene oxides such as1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide,1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.

In order to convert a carbodiimide group-containing polymer into anaqueous polymer, a hydrophilic segment is provided in the molecularstructure of the carbodiimide group-containing polymer. For example, anaqueous polymer containing a carbodiimide group can be obtained byproviding a hydrophilic segment having a functional group which hasreactivity with an isocyanate group. Usable as the hydrophilic segmentare: quaternary ammonium salts of dialkylamino alkylamine (e.g.,quaternary ammonium salts of 2-dimethylaminoethanol); quaternary saltsof dialkylamino alkylamine (e.g., 3-dimethylamino-n-propylamine); alkylsulfonic acid salts having at least one reactive hydroxyl group (e.g.,sodiumhydroxypropanesulfonate); a mixture of polyethylene oxide orpolyethylene oxide, whose terminal is capped with an alkoxy group, and apolypropylene oxide (e.g., polyethylene oxide whose terminal position iscapped with a methoxygroup or an ethoxy group).

As an aqueous cross-linking agent containing an epoxy group, there areexemplified sorbitol polyglycidyl ether, glycerol triglycidyl ether,polyglycerol polyglycidylether trimethylolpropane triglycidyl ether,poly(ethyleneglycol)diglycidyl ether, poly(propyleneglycol)diglycidylether, phenol ethyleneoxide glycidyl ether, and lauryl alcoholethyleneoxide glycidyl ether or the like. In addition to the above,mentioned as examples are: a water-soluble epoxy resin obtained byreacting a carboxy compound, which is obtained through a reactionbetween a polyoxyethylene polyol compound and an acid anhydridecompound, and an epoxy resin having two or more epoxy groups in itsmolecules; and a self-emulsifiable epoxy resin composition obtained bymixing the water-soluble epoxy resin and the epoxy resin having two ormore epoxy groups in its molecules. Such resins can be obtained forexample under the tradenames of XZ 92533.00, XZ 92598.00 and XZ 92446.00from The Dow Chemical Company, Midland, Mich. Examples of the anhydridecompound include, but not particularly limited to, preferably aromaticanhydrides such as phthalic anhydride, trimellitic anhydride, andpyromellitic anhydride; and cyclic aliphatic anhydrides such as maleicanhydride, succinic anhdyride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinicanhdyride, hexahydrophthalic anhydride, and methyl hexahydrophthalicanhydride. There is no limitation on the epoxy resin having two or moreepoxy groups in its molecules, and all known epoxy resins with an epoxyfunctionality of greater or equal to two can be used. Examples arepolyglycidyl ether obtained from epichlorohydrin and a polyhydriccompound such as, phenol novolac, and cresol novolac bisphenol A,bisphenol F, bisphenol S, resorcinol, hydroquinone or catechol; alkyleneoxide-added bisphenol A; polyalcohols such as polypropylene glycol,1,6-hexanediol, trimethylol propane, glycerin, cyclohexanedimethanol;and polyglycidyl ester and polyglycidyl amine of polycarboxylic acidssuch as adipic acid, phthalic acid, dimer acid and the like.

Aqueous cross-linking agent containing an isocyanate group are, forexample: polyisocyanate mainly containing at least one member selectedfrom the group consisting of an isocyanurate group-containingpolyisocyanate, an urethodione group-containing polyisocyanate, anurethodione group/isocyanurate group containing polyisocyanate, anurethane group containing polyisocyanate, an allophanate groupcontaining polyisocyanate, a biuret group containing polyisocyanate, acarbodiimide group containing polyisocyanate, and an uretodione groupcontaining polyisocyanate, each of which contains 1,6-hexamethylenediisocyanate and/or isophorone diisocyanate as a raw material; and aself-emulsifiable polyisocyanate obtained by reacting a hydrophilicsurfactant having at least one active hydrogen group which can reactwith an isocyanate group or polyethylene ether alcohol containing atleast three poly-ethylene oxide units with fatty acid ester in which thesum of the number of carbons of fatty acid and a hydroxyl containingcompound as raw materials is 8 or more and which has at least one activehydrogen group which can react with an isocyanate group. In addition tothe above, an urethane group-containing polyisocyanate obtained byreaction between 1,6-hexamethylenediisocyanate and/or an isophoronediisocyanate and an active hydrogen group-containing compound orpolyisocyanate obtained by an allophanatization reaction,carbodiimidization reaction, uretodionization reaction, andbiuretization reaction of these diisocyanate compounds can be mentioned.

Examples of suitable crosslinking agents containing an aldehyde arewater dispersed or waterdispersible or water-soluble phenol formaldehyderesins, amino formaldehyde resins or combinations thereof.

Phenol formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with phenols. Preferred aldehdydes butnot exclusive are formaldehyde and acetaldehyde. A large variety ofphenols can be used such as but not exclusive phenol, cresol,p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol,cyclopentylphenol, cresylic acid, bisphenol-A, bisphenol-F and the likeand combinations thereof. Also acid functional phenols could be used inmaking phenol formaldehyde resins. The crosslinkers can be unetherifiedor etherified with alcohols or polyols. These phenol formaldehyde resinsmay be soluble or self-emulsifiable in water or can be stabilized by useof colloid stabilizers such as polyvinyl alcohol.

Amino formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with amino or amido group containingmolecules. Exemplary aldehydes include, but are not limited to,formaldehyde and acetaldehyde. A large variety of amino or amido groupcontaining molecules can be used such as but not exclusive urea,melamine, benzoguanamine, acetoguanamine, glycoluril and the like.Suitable amino crosslinking resins include melamine-formaldehyde,urea-formaldehyde, benzoguanamine-formaldehyde,acetoguanamine-formaldehyde, glycoluril-formaldehyde resins. Also themethylol groups of an amino formaldehyde resin can be partially or fullyetherified with at least one of the groups of monohydric aliphaticalcohols such as methanol and/or n-butanol. These amino formaldehyderesins may be soluble or self-emulsifiable in water or can be stabilizedby use of colloid stabilizers such as polyvinyl alcohol can be used tostabilize the amino formaldehyde dispersions.

Commercially available amino-formaldehyde resins which are water solubleor water dispersible and useful for the instant purpose include Cymel™301, Cymel™ 303, Cymel™ 370, and Cymel™ 373 (all being products of CytecSurface Specialties, Brussels, Belgium). Other aldehydes used to reactwith the amino compound to form the resinous material are crotonicaldehyde, acrolein, or compounds which generate aldehydes, such ashexamethylene-tetramine, paraldehyde, and the like.

Another class of crosslinking agents for carboxylic acid groups arewater-soluble hydroxyalkylamide crosslinkers such asBis(N,N′-dihydroxyethyl)adipamide and the like. Such compounds arecommercially available under the tradename of PRIMID™ crosslinker resinsfrom EMS-PRIMID in Switzerland, for example PRIMID™ XL-522, PRIMID™SF-4510 and PRIMID™ QM-1260

The one or more crosslinking agents may be added to the aqueousdispersion as part of the aqueous dispersion formulation process; or inthe alternative, the one or more crosslinking agents may be added to theaqueous dispersion post dispersion formulation process.

In one embodiment, depending on the type of food or beverage which is tobe contained in a coated container, and on required coating propertiesit may be beneficial to combine several crosslinkers or somecrosslinkers may be more suited than others. Some crosslinkers may notbe suited for all applications. Some crosslinkers may require theaddition of catalysts for proper cure.

Crosslinkers will help to build thermoset networks, which is indicatedby higher values of MEK Double Rubs compared to an identical formulationnot containing the crosslinker.

Forming the Dispersion

The aqueous dispersion can be formed by any number of methods recognizedby those having skill in the art. Dispersion equipment can be operatedin batch, semi-batch, or continuous mode. Examples of mixers includerotor-stator, microfluidizer, high pressure homogenizer, ultrasonic,impinging jet, Cowles™ blade, planetary mixers, and melt kneadingdevices such as extruders.

In one embodiment, one or more polyethylene terephthalate resins, one ormore stabilizing agents comprising a second polyester are melt-kneadedin an extruder along with water and optionally one or more neutralizingagents, such as ammonia, potassium hydroxide, amine, or a combination oftwo or more, to form a dispersion. In another embodiment, one or morepolyethylene terephthalate resins, one or more stabilizing agentscomprising a second polyester are compounded, and then melt-kneaded inan extruder in the presence of water, and optionally one or moreneutralizing agents thereby forming a dispersion. In some embodiments,the dispersion is first diluted to contain from 1 to 20 percent, e.g., 1to 5 percent or 1 to 3 percent, by weight of water, and then,subsequently, further diluted to comprise from 15 to 90 percent byweight of water, based on the weight of dispersion. In one embodiment,further dilution may be accomplished via a solvent.

In one embodiment, the dispersion is free of any solvent. Anymelt-kneading means known in the art may be used. In some embodiments, akneader, a BANBURY® mixer, single-screw extruder, or a multi-screwextruder, e.g. a twin screw extruder, melt pump in connection with arotor stator is used. A process for producing the dispersions inaccordance with the present invention is not particularly limited. Forexample, an extruder, in certain embodiments, for example, a twin screwextruder, is coupled to a back pressure regulator, melt pump, or gearpump. Exemplary embodiments also provide a base reservoir and an initialwater reservoir, each of which includes a pump. Desired amounts of baseand initial water are provided from the base reservoir and the initialwater reservoir, respectively. Any suitable pump may be used, but insome embodiments, for example, a pump that provides a flow of about 150cc/min at a pressure of 240 bar is used to provide the base and theinitial water to the extruder. In other embodiments, a liquid injectionpump provides a flow of 300 cc/min at 200 bar or 600 cc/min at 133 bar.In some embodiments, the base and initial water are preheated in apreheater.

One or more polyethylene terephthalate resins, in the form of, forexample, pellets, powder, or flakes, are fed from the feeder to an inletof the extruder where the resin is melted or compounded. One or moreadditional components may optionally be fed simultaneously with one ormore polyethylene terephthalate resins into the extruder via the feeder;or in the alternative, one or more additional components may becompounded into one or more polyethylene terephthalate resins, and thenfed into the extruder via the feeder. In the alternative, additional oneor more additional components may optionally further be metered via aninlet prior to the emulsification zone into the molten compoundcomprising one or more polyethylene terephthalate resins. In someembodiments, the stabilizing agent comprising a second polyester isadded to one or more polyethylene terephthalate resins through and alongwith the one or more polyethylene terephthalate resins and in otherembodiments, the stabilizing agent comprising a second polyester isprovided separately to the twin screw extruder. The resin melt is thendelivered from the mix and convey zone to an emulsification zone of theextruder where the initial amount of water and base from the water andbase reservoirs are added through an inlet. In some embodiments,stabilizing agent comprising a second polyester may be addedadditionally or exclusively to the water stream. In some embodiments,further dilution water may be added via water inlet from water reservoirin a dilution and cooling zone of the extruder. Typically, thedispersion is diluted to at least 30 weight percent water in the coolingzone. In addition, the diluted mixture may be diluted any number oftimes until the desired dilution level is achieved. In some embodiments,the dispersion is further cooled after exiting the extruder by the useof a suitable heat exchanger. In other embodiments, water is not addedinto the twin screw extruder but rather to a stream containing the resinmelt after the melt has exited from the extruder. In this manner, steampressure build-up in the extruder is eliminated and the dispersion isformed in a secondary mixing device such as a rotor stator mixer.

In another embodiment, the aqueous dispersion can be formed in acontinuous high shear mixer without the use of a melt kneading extruder.In this embodiment, the first stream comprising one or more liquid ormolten polyethylene terephthalate resins is supplied to a continuoushigh shear mixer from a suitable liquid pump for example, a syringepump, gear pump, or progressive cavity pump. The first stream is flowedthrough a first conduit and merged continuously with a second streamcontaining a continuous aqueous phase that is flowed through a secondconduit. The first and second streams are merged into a disperser in thepresence of a stabilizing agent comprising a second polyester withoptional neutralizing agent. The agents can be added to either the firstor second stream, or as a separate stream. A third stream comprisingwater can be added downstream from the disperser. The flow rates of thestreams are adjusted to achieve a dispersion having the desired amountof polymer phase and percent solids. The disperser can be any one of anumber of continuous inline mixers, for example, an IKA high-shearmixer, Oakes rotor stator mixer, Ross mixer, Silverson mixer, orcentrifugal pump. The rpm setting of the disperser can be used to helpcontrol the particle size of the dispersed hydrophobic phase in thedispersion. The system can be heated to provide the polymer andneutralizer components at a suitable viscosity for pumping. Steamformation is reduced by controlling the pressure through the use of abackpressure regulator, gear pump, metering pump, or other suitabledevice near the exit of the process. In some embodiments, the dispersionis further cooled after exiting the disperser by the use of a suitableheat exchanger.

In another embodiment, the aqueous dispersion can be formed in a batchor semi-batch high shear mixer where the mixer may, for example, bedisposed within a pressurized tank to, for example, reduce steamformation. All or at least a portion of the dispersion is removed fromthe tank during processing, and optionally cooled by the use of asuitable heat exchanger.

During the preparation of the aqueous dispersion, optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, mica, calciumcarbonate, barium sulfate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more dyes; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or more defoamers;optionally one or more preservatives, e.g. biocides, mildewcides,fungicides, algaecides, and combinations thereof; optionally one or morethickeners, e.g. cellulosic based thickeners such as hydroxyethylcellulose, hydrophobically modified alkali soluble emulsions (HASEthickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modifiedethoxylated urethane thickeners (HEUR); or optionally one or moreadditional neutralizing agents, e.g. hydroxides, amines, ammonia, andcarbonates may be added to the aqueous dispersion formulation; or in thealternative, may be added to the dispersion post dispersion formulationprocess.

During the preparation of the aqueous dispersion, one or morecrosslinking agents may also be added to the aqueous dispersionformulation; or in the alternative, may be added to the dispersion postdispersion formulation process.

Optionally during the dispersion of the one or more polyethyleneterephthalate resins, another polymer dispersion or emulsion may be usedas a portion of the aqueous phase of the dispersion. Examples include,but are not limited to, acrylic, epoxy, polyester, polyurethane,polyolefin, polyamide, alkyd, and the like containing dispersions,emulsions, suspensions, colloidal suspensions.

In one embodiment, the method for producing the inventive aqueousdispersion comprises the steps of: (1) selecting one or morepolyethylene terephthalate resins; (2) selecting one or more stabilizingagents comprising at least one second polyester having an acid numberequal to or greater than 15, for example greater than 20; (3) selectingone or more neutralizing agents; (4) melt-blending said one or morefirst polyesters, one or more stabilizing agents in the presence ofwater and one or more neutralizing agents; (4) thereby producing anaqueous dispersion having a solid content of 10 to 74 percent, based onthe total weight of the dispersion.

Coating Applications and Forming Coated Containers or Closure Devices

The aqueous dispersion and/or coating composition derived therefrom maybe used on any suitable substrate including, but not limited to metal,wood, plastic, leather, glass, concrete, and the like. In one embodimentthe aqueous dispersion and/or coating derived therefrom may be used. Inone embodiment the aqueous dispersion and/or coating derived therefrommay be used, for example, in container, e.g. can, coating application,or closure device coating application. Such coated container devicesinclude, but are not limited to, cans such as beverage cans, food cans;aerosol containers such as those for non-food products, e.g. hair spray,hair dye, or color spray lacquers; drums; kegs; pails; decorative tins;open trays; tubes, bottles, monoblocs, and the like. The coated articlessuch as closure devices include, but are not limited to, caps, lids suchas thin aluminum foil based lids for yogurt and butter containers, orcrown corks; closures for glass jars and bottles such as roll-onclosures, vacuum closures, pilfer-proof closures, easy peel lids for canclosures, and easy open end or conventional ends for cans. Cans may be 2piece cans or 3 piece cans. Beverage cans include, but are not limitedto, beer cans, carbonated soft drink cans, energy drink cans, isotonicdrink cans, water cans, juice cans, tea cans, coffee cans, milk cans,and the like. Food cans, include, but are not limited to, vegetablecans, fruit cans, meat cans, soup cans, ready meal cans, fish cans,edible oil cans, sauce cans and the like. Such cans may have any shapes;for example, such can may have a cylindrical shape, cubical, spherical,semi-spherical, bottle shape, elongated cubical shape, shallow or tallshape, round or rectangular shape or any other suitable shape. Thecoated articles such as container devices according to the instantinvention may be formed via any conventional method. For example, thecoated container device may be formed via stamping, drawing, redrawing,wall ironing, bending, beading, embossing, debossing, flanging, necking,stretching, blow-stretching and any other suitable conventional method.Such methods are generally known to those having ordinary skill in theart. The aqueous dispersion and/or coating composition derived therefrommay, for example, be applied to a substrate, e.g. metal sheet or metalfoil, and then the coated substrate may be formed into a coatedcontainer device or a coated closure device. In the alternative, asubstrate may be formed into a container device or a closure device, andthen the container device or the closure device is coated with one ormore aqueous dispersions and/or coating composition derived therefrom toform the coated container device or coated closure device. The coatingmay be applied via any method; for example, via roller coating, spraycoating, powder coating, dip coating, electrodeposition coating,printing, wash coating, flow coating, curtain coating.

The substrate comprises one or more metals including, but not limitedto, aluminum and aluminum alloys, electrolytic tinplate cold rolled lowcarbon mild steel (“ETP”), electrolytic chromium/chromium oxide coatedcold rolled low carbon mild steel (ECCS), and any other pre-treatedsteel, or one or more polymers such as one or more polyolefins, e.g.polyethylene and/or polypropylene. Pretreatment may include, but is notlimited to, treatment with phosphoric acid, zirconium phosphate,chromium phosphate, and the like as well as silanes for reasons such asprimary corrosion protection and improved adhesion. The substrate maycomprise a sheet, strip or a coil. The substrate may comprise one ormore layers, and each layer may have a thickness in the range of from0.01 μm to 2 mm; for example, from 0.01 μm to 1.5 mm; or in thealternative, from 0.01 μm to 1 mm; or in the alternative, from 0.01 μmto 0.5 mm; or in the alternative, from 0.01 μm to 0.2 mm; or in thealternative, from 0.01 μm to 0.1 mm or in the alternative, from 0.01 μmto 100 μm; or in the alternative, from 0.01 μm to 50 μm; or in thealternative, from 1 μm to 50 μm; or in the alternative, from 1 μm to 15μm. The substrate may be pre-coated with one or more pre-coatingcompositions. Such pre-coating compositions may optionally furtherinclude, but are not limited to, one or more resin binders, one or moreresin crosslinkers, one or more solvents, one or more additives, and oneor more pigments. Exemplary resin binders include, but are not limitedto, epoxy, polyester, polyvinyl chloride containing organosols/vinyls,phenolic, alkyd, oleoresin, acrylic resin, and the like. Exemplarycrosslinkers include, but are not limited to, phenol-formaldehyderesins; amino-formaldehyde resins including but not limited tourea-formaldehyde, melamine formaldehyde, benzoguanamine formaldehyde;anhydride resins, blocked isocyanate resins and epoxy groups containingresins, including but not limited to, epoxy resins, epoxy groupscontaining polyesters, acrylic resins, vinyl resins or the like.Exemplary solvents and thinners include, but are not limited to, glycolethers, alcohols, aromatics, e.g. aromatic hydrocarbons, white spirit,branched ketones and esters. Exemplary additives include, but are notlimited to, catalysts, lubricants, wetting agents, defoamers, flowagents, release agents, slip agents, anti-blocking agents, additives tomask sulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters. Pigments include, but arenot limited to titanium dioxide, zinc oxide, aluminum oxide, zinc andaluminum. The substrate may also be pre-coated with one or morepre-coated laminate compositions. Such compositions may, for example,include polyethylene, polypropylene, or polyester compositions, and maybe applied either as a film via film lamination process ormelt-extrusion coating process onto the metal surface.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried via any conventional drying method. Such conventional dryingmethods include but, are not limited to, air drying, convection ovendrying, hot air drying, and/or infrared oven drying. During the dryingprocess, crosslinking of one or more base polymers, stabilizing agents,or combinations thereof, involving one or more the crosslinking agents,may occur. Additional cure might occur by radiation cure, e.g.electron-beam cure. The one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at any temperature; for example, it may be driedat a temperature in the range of equal or greater than the melting pointtemperature of the first polyester; or in the alternative, it may bedried at a temperature in the range of less than the melting point ofthe stabilizing agent comprising a second polyester. The one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be dried at atemperature in the range of about 60° F. (15.5° C.) to about 700° F.(371° C.) for a period of less than about 40 minutes, for example, lessthan 20 minutes, or less than 10 minutes, or less than 5 minutes, orless than 2 minutes, or less than 1 minute, or less than 20 seconds. Allindividual values and subranges from about 60° F. (15.5° C.) to about700° F. (371° C.) are included herein and disclosed herein; for example,the one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried at a temperature in the range of about 60° F. (15.5° C.) to about500° F. (260° C.) for a period of less than about 40 minutes, forexample, less than 20 minutes, or less than 10 minutes, or less than 5minutes, or less than 2 minutes, or less than 1 minute, or in thealternative, the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at a temperature in the range of about 60° F.(15.5° C.) to about 450° F. (232.2° C.) for a period of less than about40 minutes, for example, less than 20 minutes, or less than 10 minutes,or less than 5 minutes, or less than 2 minutes, or less than 1 minute.The temperature of the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be raised to a temperature in the range of equal orgreater than the melting point temperature of the base polymer for aperiod of less than about 40 minutes. All individual values andsubranges from less than about 40 minutes are included herein anddisclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 20minutes, or in the alternative, the temperature of the one or moreaqueous dispersions applied and/or coating composition derived therefromto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 5minutes, or in another alternative, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period in the range of about0.5 to 300 seconds. In another alternative, the temperature of the oneor more aqueous dispersions and/or coating composition derived therefromapplied to the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than 40 minutes. All individualvalues and subranges from less than about 40 minutes are included hereinand disclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than about 20 minutes, or inthe alternative, the temperature of the one or more aqueous dispersionsand/or coating composition derived therefrom applied to the at least onesurface of the substrate may be raised to a temperature in the range ofless than the melting point temperature of the first polyester for aperiod of less than about 5 minutes, or in another alternative, thetemperature of the one or more aqueous dispersions applied and/orcoating composition derived therefrom to the at least one surface of thesubstrate may be raised to a temperature in the range of less than themelting point temperature of the first polyester for a period in therange of about 0.5 to 300 seconds.

The coated substrate may further be coated with one or more conventionalcoating compositions, or it may further be laminated to one or moreother layers. Such conventional coating compositions are generally knownto person of ordinary skill in the art, and they may include, but arenot limited to, epoxy resin coating compositions, acrylate based coatingcompositions, and polyester based coating compositions. The laminationprocess is generally known, and exemplary lamination layers may include,but are not limited to, polyester laminates, polyolefin based laminatessuch as polypropylene laminates.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to at least one surface of a substrate, for example apre-coated substrate, as one or more crosslinked coating layers may havea cross cut adhesion, before retort, rating of at least 3B; for example,4 B or 5B, measured according to ASTM-D 3359-08. The one or more aqueousdispersions and/or coating composition derived therefrom applied to atleast one surface of a substrate as one or more crosslinked coatinglayers may have a wedge bend pass rating of at least 50 percent, forexample, at least 70 percent, or in the alternative, at least 80percent, or in the alternative, at least 90 percent, measured via aGardner “COVERALL” Bend Tester IG 1125.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention. The examples of theinstant invention demonstrate that the one or more aqueous dispersionsapplied to at least one surface of a metal substrate provide forimproved coating layer flexibility as well as coating layer adhesion tothe metal substrate.

Description of Formulation Components

Crylcoat 1510 is an aromatic polyester having a T_(g) of approximately58° C., a melt viscosity of 8500 Poise at 200 C, an acid number of 71 mgKOH/g and a hydroxyl number of <20 mg KOH/g, available from CytecIndustries.

Cadence GS4 is a PET type copolyester polyester having a T_(g) of 80°C., and an intrinsic viscosity of approximately 0.59 Dl/g, availablefrom Eastman Chemical. CYMEL 303 crosslinking agent is a commercialgrade of hexamethoxymethylmelamine supplied in liquid form at >98%non-volatile, a clear viscous liquid with a viscosity of 2600-5000centipoise, available from Cytec Industries.

NACURE 5925 is an amine neutralized DDBSA catalyst, which is a clear,light amber liquid supplied as 25% active and with a typical recommendeduse level of 0.5 to 2.0% as supplied on total resin solids, availablefrom King Industries.

Eastman AQ 55s is a sulfonated polyester having a T_(g) of approximately55° C., a melt viscosity of 42000 Poise at 200 C, an acid number<2 mgKOH/g and a hydroxyl number<10 mg KOH/g, available from EastmanChemical.

Preparation of Inventive Aqueous Dispersion Example A and B

Aqueous dispersions A and B were prepared according to the followingprocedures based on the formulation components listed in Table 1. Theone or more polyethylene terephthalate resins, and stabilizing agentwere fed into a 25 mm diameter twin screw extruder by means of separatecontrolled rate feeders. In the extruder the one or more polyethyleneterephthalate resins and stabilizer were melted, mixed and forwarded.The extruder temperature profile was initially set to 150° C. prior tothe addition of the initial water and neutralizing agent. After theaddition of initial water and neutralizing agent the temperature waslowered to 120° C. across the barrel. In Example A DMEA, 2-dimethylamino ethanol (100%) (CAS No. 108-01-0) was used as the neutralizingagent. Example B used no neutralizing agent. The extruder speed wasapproximately 450 rpm. Amine base and initial water were mixed togetherand fed to the extruder at the initial water introduction point inexample A, and only water was fed into the extruder at the initial waterintroduction point in example B. The dilution water was fed via a secondpump, and it was introduced into the dilution zone of the extruder. Theinitial water and dilution water streams were optionally pre-heated tothe extruder temperature. At the extruder outlet, a back-pressureregulator was used to adjust to a suitable pressure inside the extruderbarrel to prevent steam formation at the operating temperature. Theresulting dispersions were cooled and filtered through a 200 micronfilter. Inventive aqueous dispersion example A was tested for itsproperties, and the results are reported in Table 3.

TABLE 1 Stabilizing Agent Average Comprising Initial Dilution ParticlePolyethylene Second Neutralizing Water Water Size Aqueous TerephthalatePolyester Agent Rate Rate Diameter Dispersion Resins (g/min) (g/min)(ml/min) (ml/min) (ml/min) (microns) Inventive Cadence GS4 Crylcoat 1510DMEA 10.7 65 1.1 Example A (60.5) (15.1) (2.3) Inventive Cadence GS4Eastman AQ n/a 12.3 70 1.0 Dispersion (64.3) 55 (0)   B (11.3)

TABLE 2 Stabilizing Agent Average Comprising Measured ParticlePolyethylene Second Neutralizing Total Size Aqueous TerephthalatePolyester Agent Water Solid % Diameter Dispersion Resins (W %) (W %)) (W%)) (W %)) (W %) Neutralization pH (microns) Inventive Cadence GS4Crylcoat DMEA 49.30 49.27 120 9.09 1.1 Example A (39.38) 1510 (1.48)(9.84) Inventive Cadence GS4 Eastman n/a 52.12 51.03 n/a 6.82 1.0Example B (40.72) AQ 55 0% (7.16)

Comparative Coating Composition Examples 1 and 2

Dynapol L952 was dissolved into a 1:1 blend by weight of toluene and PMacetate (1-methoxy-2-acetoxypropane) at 70° C. to produce a 40% weightsolids solution. This procedure was performed in 5 liter round bottomflask under constant agitation with a rod stirrer and a heating mantle,resulting in ˜3500 g of solution. After cooling to room temperature(˜25° C.), this solution was then mixed with Cymel™ 303LF,hexamethoxymethylmelamine resin (Cytec Industries), as a crosslinkingagent, Nacure 5925, amine neutralized dodecylbenzene sulfonic acid (KingIndustries), as a catalyst, and PM acetate to reduce solids in a 2 oz.glass jar using a tumbler at room temperature, approximately 25° C.,overnight (18-24 hrs) to yield the comparative coating compositionexample 1. Following the same procedure described above as incomparative coating composition example 1, Dynapol L952 solvent basedsolution was mixed with Cymel 303LF, Crylcoat 1510-0, DMEA, for amineneutralization, Nacure 5925, and PM acetate to form comparative coatingcomposition example 2. Coatings formulation components for comparativecoating composition examples 1 and 2 are listed in Table 3.

TABLE 3 Dynapol L952 SB Crylcoat Cymel Nacure Extra Total Solution1510-0 303LF DMEA 5925 PMA Formulation Total Coating Amount AmountAmount Amount Amount Amount Amount Formulation Composition (g) (g) (g)(g) (g) (g) (g) % Solids Comparative 25.00 0.00 4.29 0.00 0.07 18.5047.86 30.00 Example 1 Comparative 25.00 2.50 4.29 0.28 0.09 25.74 57.9029.64 Example 2Coating Application

Inventive Aqueous dispersion example A was applied to a aluminum metalpanel using a draw down bar and baked for 30 minutes at 120° C. to givea coating with an excellent balance of hardness and flexibility alongwith good chemical resistance and adhesion to metal, as shown in Table4.

TABLE 4 Film Thickness (mils)-Average 5 1.34 20 deg Gloss ave on Alpanel 99.4 Pencil Hardness HB Konig Hardness [sec] 24 hrs after bake 216X-Hatch Adhesion 5B MEK Resistance [double rubss] First cut throughcoating 10 Acid Etch Test 1^(st) visible defect (4) ° C. 50 Severedefect (1) ° C. 76 Rating @ 60° C. 5 Rating @ 70° C. 2 SteelPanels/Impact Resistance Direct (in-lbs) 130 Indirect (in-lbs) 130Chemical Tests (24 hr covered) Water 4 Antifreeze 5 Power Steering Fluid5 Windshield Wash Solvent 5 Used Motor Oil 5 Bleach 6% 5 Glass Cleaner 35% NaOH 5 5% Acetic Acid 5 1-5 scale, where 5 is bestInventive Coating Compositions 1-4

Inventive aqueous dispersion A was mixed with Cymel™ 303LF,hexamethoxymethylmelamine resin (Cytec), as a crosslinking agent, andNacure 5925, amine neutralized dodecylbenzene sulfonic acid (KingIndustries), as a catalyst in a 2 oz. glass jar using a tumbler at roomtemperature, approximately 25° C., overnight (18-24 hrs) to yieldInventive Coating compositions 1-4. Coatings formulation components arelisted in Table 5.

Inventive Coating Compositions 5-7

Inventive aqueous dispersion B was mixed with Cymel™ 303LF,hexamethoxymethylmelamine resin (Cytec Industries), as a crosslinkingagent, and Nacure 5925, amine neutralized dodecylbenzene sulfonic acid(King Industries), as a catalyst in a 2 oz. glass jar using a tumbler atroom temperature, approximately 25° C., overnight (18-24 hrs) to yieldInventive Coating compositions 5-7. Coatings formulation components arelisted in Table 5.

TABLE 5 Total Total Cymel Nacure Formu- Formu- Inventive Dis- Dispersion303LF 5925 lation lation Coating per- Amount Amount Amount Amount %Composition sion (g) (g) (g) (g) Solids Inventive A 40.00 — — 40.0049.27 Example 1 Inventive A 40.00 1.04 0.10 41.14 50.68 Example 2Inventive A 40.00 2.19 0.11 42.30 52.03 Example 3 Inventive A 40.00 8.450.14 48.59 58.24 Example 4 Inventive B 40.00 — — 40.00 51.03 Example 5Inventive B 40.00 1.07 0.11 41.18 52.44 Example 6 Inventive B 40.00 2.270.11 42.38 53.78 Example 7Coating Application

A tin plate panel, provided by Rasselstein, having grade TS-245 standardfinish, with approximately 10 cm to 20 cm size was cleaned with acetone,and then dried. About 3 grams of the inventive coating compositions 1-4were applied individually to the tin plate panel via a 35 micron (1.4mil #14) wirewound drawdown bar thereby coating one surface of the tinplate panel. Subsequently, the panel was placed into a convection ovento be cured for 10 minutes at 200° C. The coated tin plate panels weretested for wedge bend, cross cut adhesion before sterilization, andcross cut adhesion and blush after sterilization according to theprocedures described below. Aluminum panels (can stock clean aluminummeasuring 0.009×4″×12″ from All Foils), cleaned with acetone and dried,were used for coating thickness and MEK DR (methyl ethyl ketone doublerub) evaluation. The results are reported in Table 6-9.

TABLE 6 Crosscut Crosscut Inventive Coating MEK Wedge Adhesion AdhesionRetort Coating Thickness Double Bend Before Retort After Retortresistance Composition (mil) Rubs (% Pass) in Water in Water in WaterInventive 0.41-0.45 5 100 5B 5B 3 Example 1

TABLE 7 Crosscut Crosscut Retort Inventive Adhesion Adhesion resistanceCoating Before Retort in After Retort in in Lactic Composition LacticAcid Lactic Acid Acid Inventive 5B 5B 3 Example 1

TABLE 8 Crosscut Crosscut Coating MEK Wedge Adhesion Adhesion RetortCoating Thickness Double Bend Before Retort After Retort ResistanceComposition (mil) Rubs (% Pass) in Water in Water in Water Inventive0.29-0.34 150+ 100 5B 5B 3 Example 2 Inventive 0.25-0.37 150+ 100 5B 5B3 Example 3 Inventive 0.37-0.43 150+ 100 5B 0B 2 Example 4 Inventive0.42-0.48 5 76 — — — Example 5 Inventive 0.36-0.43 150+ 100 — — —Example 6 Inventive 0.42-0.45 150+ 100 — — — Example 7 Comparative0.35-0.45 65 84 5B 5B 5 Example 1 Comparative 0.35-0.45 60 76 5B 5B 4Example 2

TABLE 9 Crosscut Crosscut Adhesion Adhesion Retort Before AfterResistance Coating Coating Retort in Retort in in Lactic CompositionFormulation Lactic Acid Lactic Acid Acid Inventive 2 5B 3B 3 Example 2Inventive 3 5B 0B 3 Example 3 Inventive 4 5B 0B 3 Example 4 Comparative5 5B 0B 4 Example 1 Comparative 6 5B 2B 4 Example 2

Test Methods

Test methods include the following:

Particle Size Measurement

The average particle size was measured by a Coulter LS-230 particle sizeanalyzer (Beckman Coulter Corporation).

Film thickness of the coatings was determined by following ASTM D 1186.

Impact resistance was measured according to ASTM D5420 using a Gardnerimpact tester (Paul N. Gardner Co).

Konig hardness of the coating films were determined according to ASTM-D4366 (1995) by using a pendulum hardness tester and is reported inseconds.

The pencil hardness of the coating films was measured by following ASTMD 3363 (2005) using pencils with leads ranging in hardness from 6B to 4H(Paul N. Gardner Co).

The solvent resistance of the coating films was measured according toASTM D4752 using methyl ethyl ketone (MEK) as the solvent with thenumber of rubs reported before a blister in or breakthrough of the filmoccurs. The rubs are counted as a double rubs, i.e. one rub forward andone rub backward constitutes a double rub. This test method is used todetermine the curing degree of coating film and its resistance to aspecific solvent.

Gloss was measured according to ASTM D523 using a BYK Micro-Tri-Glossmeter.

The acid etch resistance of the coating was determined by using a BYKChemie gradient temperature oven and was reported as the lowesttemperature (in ° C.) that a 10% solution of H₂SO₄ would either mar thefilm (1st visible defect) or cut through to the substrate (severedefect) if left on the coating for 15 minutes. The higher thetemperature reported, the more resistant the coating was to acid.

The film appearance was also rated at 60 and 70° C. (1-5 scale, where 5is best).

The resistance to a variety of chemicals was measured by placing a 1 mldrop of the chemical on the coating and allowing it to stand for 24hours (covered to prevent evaporation) after which time the appearanceof the film was rated (1-5 scale, where 5 is best).

Cross-Cut Adhesion before Retort

Cross-cut adhesion is measured according to ASTM-D 3359-02, measuringadhesion by tape test, Method B., using an Erichsen cross-cut tester EPT675R. This method provides the procedure for assessing the adhesion ofcoating films to metallic substrates by applying and removing a tape(grade: TESA 4124 clear) over the cuts made in the film. Place thecentre of a piece of tape over the grid and in the area of the gridsmooth into place by a finger. To ensure good contact with the film rubthe tape firmly. Within 90±30 seconds of application, remove the tape byseizing the free end and rapidly (not jerked) pulling it off at as closeto an angle of 180 degrees as possible. Inspect the grid area forremoval of coating from the substrate or from a previous coating usingthe illuminated magnifier. Rate the adhesion in accordance with thefollowing scale rating:

5B The edges of the cuts are completely smooth; none of the squares ofthe lattice is detached. 4B Small flakes of the coating are detached atintersections; less than 5% of the area is affected. 3B Small flakes ofthe coating are detached along the edges and at intersections of cuts.The area affected is 5-15% of the lattice. 2B The coating has flakedalong the edges and on parts of the squares. The area affected is 15-35%of the lattice. 1B The coating has flaked along the edges of cuts inlarge ribbons and whole squares have detached. The area affected is35-65% of the lattice. 0B Flaking and detachment is worse than 1BCross-Cut Adhesion after Retort

In addition to testing cross cut adhesion on the dry panels prior towater retort exposure, a cross-cut adhesion test is performed within anhour of being removed from the autoclave and rated for adhesion asdescribed in the cross cut adhesion section. The adhesion is rated inaccordance with the following scale rating:

5B The edges of the cuts are completely smooth; none of the squares ofthe lattice is detached. 4B Small flakes of the coating are detached atintersections; less than 5% of the area is affected. 3B Small flakes ofthe coating are detached along the edges and at intersections of cuts.The area affected is 5-15% of the lattice. 2B The coating has flakedalong the edges and on parts of the squares. The area affected is 15-35%of the lattice. 1B The coating has flaked along the edges of cuts inlarge ribbons and whole squares have detached. The area affected is35-65% of the lattice. 0B Flaking and detachment is worse than 1BRetort Resistance (Water)

The coated panels were immersed in water in individual pressurizableglass beakers that were contained in a secondary container tray, andplaced into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclave model 1Z-TUT-EZ-10 where they were retorted at 129° C. for 30 minutes. Thepanels were removed, and dried. The coating appearance was then rated ona scale of 1-5 (5—best, 1-worst) as determined by blush (a whitishappearance of the coating). as shown below.

5 No Blush 4 Very Slight blush 3 Slight blush 2 Blush 1 Strong BlushRetort Resistance (Lactic Acid)

The coated panels were immersed in 2% lactic acid in individualpressurizable glass beakers that were contained in a secondary containertray, and placed into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclavemodel 1 Z-TUT-EZ-10 where they were retorted at 121° C. for 30 minutes.The panels were removed, and dried. The coating appearance was thenrated on a scale of 1-5 (5—best, 1—worst) as determined by blush (awhitish appearance of the coating) as shown below.

5 No Blush 4 Very Slight blush 3 Slight blush 2 Blush 1 Strong BlushMEK Double Rub

The round end of a 1.5 pound ball peen hammer was used to perform theMEK double rub test by applying a force of ˜1000-2000 g to the coating.A 4″×4″ square of cheesecloth was bound around the hammer end and soakedwith methyl ethyl ketone (MEK). The hammer was brought into contact withthe coating, and moved forth-and-back over a section measuringapproximately 6″×1″, wherein one movement forth-and-back over the wholecoating is considered one double rub. Double rubs were performed at arate of about one double rub per second. No additional pressure wasapplied onto the hammer. After every 25 double rubs, the tissue wasre-soaked. The double rub step was repeated until the coating was rubbedoff, i.e. at least a portion of the metal substrate was exposed(excluding the ½″ end sections of the testing area). In the event thatthe double rub step reached 150 double rubs, the testing was terminated,and 150+ double rubs were reported as the final results.

Wedge Bend

Wedge bend was measured via Gardner “COVERALL” Bend Tester IG 1125. Theapparatus used for this test consists of two parts to convert it to abending machine. A steel rod (mandrel) is mounted at the front of thebase. The coated test panel of 100 mm width was flexed over the 3 mm rodmandrel; thus, the coating appears on the outside of the bend. Theflexed panel was inserted in the wedge mandrel. The impacter, i.e. ametal weight, was raised to 40 centimeters height, and then dropped. Theimpacter is retrieved on its first bounce, and secured. The cylindricalfold in the panel was squeezed into a conical shape. The edge of thecoated panel was rubbed with a solution of copper sulfate (mixture of 10grams of copper sulfate, 90 grams of water and 3 grams of sulfuricacid). Anywhere the coating had been cracked; dark spots appeared,indicating failure. The length of the intact area along the length ofthe wedge bend, which is 100 mm, was measured in millimeters andexpressed as percent ok.

Coating Thickness

Coating thickness was measured according to ASTM-D 1186-93,non-destructive measurement of dry film thickness of non magneticcoatings applied to a non-ferrous base, using a Byko-Test 8500 coatingthickness gauge. The standard aluminum panel without any coating wasused for calibration. The thickness of the coating of the coated panelswas reported as the range of 10 measurements, wherein each measurementof the thickness of the coating of the coated panels was measured usinga probe for non-ferrous materials relative to the thickness of thecoating of the standard panel, i.e. zero. The measured thickness wasreported in mils.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

1. An aqueous dispersion comprising the melt blending product of: (a)from 50 to 99 percent by weight of one or more polyethyleneterephthalate resins, based on the total solid content of thedispersion; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyester(i) has a carboxylic acid group and an acid number equal to or greaterthan 15, based on the solid content of the second polyester; or (ii) isa self-dispersing sulfopolyester; (c) optionally one or moreneutralizing agents; and (d) from 15 to 90 percent by weight of water,based on the total weight of the dispersion; wherein said dispersion hasa solid content of 10 to 85 percent, based on the total weight of thedispersion, and wherein the volume average particle size of thedispersion is less than 5 microns.
 2. A method for producing a aqueousdispersion comprising the steps of: selecting one or more polyethyleneterephthalate resins; selecting one or more stabilizing agentscomprising at least one second polyester, wherein said second polyester(i) has a carboxylic acid group and an acid number equal to or greaterthan 15, based on the solid content of the second polyester; or (ii) isa self-dispersing sulfopolyester; optionally selecting one or moreneutralizing agents; melt-blending said one or more polyethyleneterephthalate resins, one or more stabilizing agents in the presence ofwater and optionally one or more neutralizing agents; thereby producingan aqueous dispersion having a solid content of 10 to 85 percent, basedon the total weight of the dispersion, and wherein the volume averageparticle size of the dispersion is less than 5 microns.
 3. A coatingcomposition comprising: the aqueous dispersion of claim 1; optionallyone or more cross-linking agents; optionally one or more cross-linkingcatalysts; optionally one or more solvents; optionally one or moreselected from the group consisting of a polyolefin dispersion, acryliclatex, alkyd dispersion, epoxy resin dispersion, polyurethanedispersion, vinyl acetate dispersion, and ethylene vinyl acetatedispersion; and optionally one or more additives.
 4. An aqueousdispersion comprising the melt blending product of: (a) from 50 to 99percent by weight of one or more polyethylene terephthalate resins,based on the total solid content of the dispersion; wherein thepolyethylene terephalate resin has a glass transition temperature(T_(g)) of at least 65° C., and an intrinsic viscosity of 0.5-1.0 Dl/g;(b) from 1 to 50 percent by weight of one or more stabilizing agentscomprising at least one second polyester, based on the total solidcontent of the dispersion, wherein said second polyester has acarboxylic acid group and an acid number equal to or greater than 20,based on the solid content of the second polyester; (c) one or moreneutralizing agents; and (d) from 15 to 90 percent by weight of water,based on the total weight of the dispersion; wherein said dispersion hasa solid content of 10 to 85 percent, based on the total weight of thedispersion, and wherein the volume average particle size of thedispersion is less than 5 microns.
 5. A coating layer comprising one ormore film layers derived from the dispersion of claim 1 or the coatingcomposition of claim
 3. 6. A coated article comprising: one or moresubstrates; at least one or more coating layers derived from thedispersion of claim 1 or the coating composition of claim
 3. 7. A methodfor making a coated article comprising the steps of: selecting asubstrate; selecting the coating composition of claim 3; applying saidcoating composition to at least one surface of said substrate; removingat least a portion of the water from said the coating composition;thereby forming one or more coating layers associated with saidsubstrate; and forming said coated substrate into a coated article.
 8. Amethod for making a coated article comprising the steps of: selecting asubstrate; forming said substrate into article; selecting the coatingcomposition of claim 3 applying said the coating composition to at leastone surface of said article; removing at least a portion of the waterfrom said the coating composition; thereby forming one or more coatinglayers associated with at least one surface of said article; and therebyforming said coated article.
 9. The aqueous dispersion of claim 1,wherein said one or more polyethylene terephthalate resins have a glasstransition temperature (T_(g)) of at least 30° C.
 10. The coated articleof claim 6, wherein said substrate is a pre-coated substrate.
 11. A canor coil coating composition comprising the coating composition of claim3.
 12. A can or coil coating composition comprising the aqueousdispersion of claim 4; optionally one or more cross-linking agents;optionally one or more cross-linking catalysts; optionally one or moresolvents; optionally one or more selected from the group consisting of apolyolefin dispersion, acrylic latex, alkyd dispersion, epoxy resindispersion, polyurethane dispersion, vinyl acetate dispersion, andethylene vinyl acetate dispersion; and optionally one or more additives.